Metallizable hexakisazo dyestuffs



United States Patent 2,958,689 METALLIZABLE HEXAKISAZO DYESTUFFS Hans-Rudolf Byland, Riehen, and Fritz Kehrer, Basel,

Switzerland, assignors to Sandoz A. G., Basel, Switzerland No Drawing. Filed Aug. 8, 1958, Ser. No. 753,869 Claims priority, application Switzerland July 1, 1954 6 Claims. (Cl. 260-144) The present application is a continuation-in-part application to our co-pending application Ser. No. 518,399, filed on June 27, 1955, now abandoned. The present invention relates to new metallizable hexakisazo dyestuffs of the formula Z OH NH: C OOH wherein one 2: represents hydrogen, the other x being a sulfonic acid group, y represents hydrogen or a sulfonic acid group, z represents COOH or OCH and R represents the radical of a monoazo compound which corresponds to the following formula and couples in the, position of the naphthalene nucleus designated by an arrow wherein v represents hydrogen, methyl, methoxy, chlorine or a sulfonic acid group, w represents hydrogen,

.chlorine, nitro, a sulfonic acid group, a sulfonic acid .has a meaning other than hydrogen, chlorine, nitro and a sulfonic acid group, the total number of sulfonic acid groups present in the hexakisazo dyestuff being at most 6.

These new hexakisazo dyestutfs are obtained when 1 mole of a disazo compound of the formula HO NH: COOH N=N u 2,958,689 Patented Nov. 1, 1960 ice wherein x, y and z possess the above named meanings, one u represents an amino group and the other urepresents an amino group, a nitro group or a readily saponifiable acylamino group, (a) is tetrazotized (provided the two substituents u are amino groups) and the resulting tetrazo compound is coupled with two moles of a monoazo compound of the formula II; (b) is diazotized (provided one of the substituents u is a nitro or a readily saponifiable acylamino group), the diazo compound is combined with 1 mole of a monoazo compound of the Formula II and the nitro or saponifiable acylamino group in the resulting tetrakisazo compound reduced or saponified, as the case may be, to the amino group, this being diazotized and the diazotetrakisazo compound thus obtained coupled with 1 mole of the same monoazo compound of the Formula II.

The reduction of the nitro to the amino group, where present as substituent u, is carried out by the agency of e.g. sodium sulfhydrate, the saponification of the alternative acylamino group being effected in an acid or alkaline medium. Readily saponifiable acylamino groups are, for example, the formyl, acetyl, oxalyl, carbomethoxyand carboethoxy-amino groups.

The monoazo compounds of the Formula II are produced by coupling diazotized 2-arnino-l-hydroxybenzenes in an acid medium with Z-phenylarnino-S-hydroxynaphthalene-7-su1fonic acids which may be substituted in the phenyl radical by methyl, methoxy, chlorine or a sulfonic acid group.

Examples of 2-amino-1hydroxybenzenes suitable for this purpose are: 2-amino-lhydroxybenzene, Z-amino-lhydroxy-4nitro-6-carboxybenzene, 2-amino-1-hydroxytor S-alkylsulfonyl-benzenes, Z-amino-l-hydroxybenzene- 4- or 5-sulfonic acid, Z-amino-1-hydroxy-6-carboxybenzene4-sulfonic acid, 2-amino-1hydroxybenzene-4- or 5- sulfonic acid amide and the derivatives methylated, ethylated, 'dimethylated and diethylated on the nitrogen atom of the sulfamide group, also Z-amino-l-hydroxy- 4-chloroor nitrobenzene-S-sulfonic acid, 2-amino-1- hydroxy--nitroor chlorobenzenel-sulfonic acid and the isomeric compounds in which the substituents in 4- and o-position are replaced by each other, further the Z-amino-lhydroxy-S-nitrobenzene, 2-amino-1-hydroxy- 4-nitroor chlorobenzene and 2-amino-1-hydroxy-4- chloro-5- or 6-nitrobenzene.

When the two substituents u in the Formula III are amino groups, the tetrazo compound obtained by treating the diamine with sodium nitrite in acid medium is coupled with 2 moles of a monoazo compound of the Formula II in an alkaline medium. To accelerate the coupling reaction it is advisable to include an organic tertiary base such as pyridine, quinoline or a technical mixture of pyridine bases in the reacting solution.

When however one of the substituents u in the Formula III is an amino group and the other is a nitro group or a readily saponifiable acylamino group, the diazo compound obtained by treating the monoamine with sodium nitrite in acid medium is coupled with 1 mole of the monoazo compound of the Formula II, then the nitro group is reduced or the acylamino group is split off, the amino group thus obtained is diazotized and the diazotetrakisazo compound is coupled with 1 mole of the same monoazo compound of the Formula II. An addition of an organic tertiary base such as pyridine, quinoline or a technical mixture of pyridine bases to the second coupling solution causes a considerable acceleration of the coupling reaction.

The new hexakisazo dyestuffs are readily soluble in Water and possess excellent building-up properties on cotton and fibers made from regenerated cellulose and a good salt controlability. They dye these fibers by the one-bath coppering and two-bath aftercoppering processes in superior gray shades of excellent fastness to light, washing, perspiration, formaldehyde and gas fumes. The dyeings are well dischargeable and possess a good stability to anticrease finishing treatments and a good ,fastof a mixture of pyridine bases and 70 parts of aqueous ammonia. The hexakisazo dyestutf is rapidly formed. After being agitated for several hours, the coupling mass is heated, the dyestuif precipitated by means of common ness to boiling in alkaline and neutral medium either in salt, filtered and dried. It is a dark powder which disopen or in closed vessels. Aftertreatment of the dyeings solves in water to give solutions of blue-green colour with salts of divalent copper in the-presence of polymeric from which cotton and fibers from regenerated cellulose substances containing imino 01' amino groups, such as are dyed in neutral gray shades. Aftertreatment-with "are described for example in U.S. Patent 2,622,075, ,is copper salts imparts to the dyeings outstanding fastness particularly valuable. to washing and persplratlon and very good .iastness to The following examples illustrate the invention. All light. parts are by weight; temperatures are in degrees cen- Example 2 tlgrade' E l 1 6.6 parts of the nitro-aminodisazo compound of the xamp e formula 6.3 parts of the diaminodisazo compound of the for- Ho 000]; vmula I l 0 CH3 HO NH; C O OH 2 =N -N=N NH: ;HiN-C -N=N N=N NH, HOs'S scan H035 are dissolved in 5.0 :parts of water and 2 parts of sodium carbonate. To this 0.7 part of sodium nitrite is added aredissolved in 80 parts of water and 2 parts of sodium and the solution dropped slowly into a mixture of 10 .carbonate. 1.4 parts of sodium nitrite are added to the parts of hydrochloric acid and parts Of The solution which is then dropped slowly into a mixture of dlazodisazo compound so formed is run into a solution .15 parts of concentrated hydrochloric acidand 50;parts of 5.2 parts .of the monoazo compound obtained by .gfjce. The tetrazo compound thus formed is transferred and coupling of diazotized Z-amino-1-hydroxy-4-methyldropwise-in the course of one hour to an ice-cooled solusulfonylbenzene with 2-phenylamino-5-hydroxynaphtha- ;ti0,n of 10.8 parts of the monoazoco-mpound obtained by 30 lene-7-sulfonic acid, 150 parts of water, 10 parts of a :acid coupling of diazotized Z-amino-l-hydroxybenzenemixture .of pyridine bases and 5.0 parts of aqueous am- 4-sulfonic acid amide with 2-phenylamino-5-hydroxymonia. The nitrotetrakisazo compound thus obtained .naphthalene-7-su1fonic acid, 150 parts of water, 10 parts is converted into the aminotetra'kisazo compound by TABLE .Example (I) (II) (III) N o. l-AminO-S-hydroxyrigphthalenesuiionicz Monoazo Compound RH 3.. l-amino-8-hydroxynaphthalene3.6-di- O,0H 2-arnino-l-hydroxy-6-carboxybenzene-4-sulfonic acid-wtacid) 2-phenylamino-5-hysulfonic acid. droxynaphthalene-7-sulionlc acid. 4 do -OCH Z-amino-l-hydroxy-4-nitrobenzenev(acid) ,2-phenylamino-5-hydroxynaphthalene-7- sulionic acid. do COOH-. Do. 6 1-amino-8hydroxynaphthalene-4.6-di- GOOH.. 2-arnin0-1-hydroxybeuzene-5-sulfonic acid amide- (acid) 2-(4-methyl)-phenylaminosulfonic acid. I -5-hydroxynaphthalene-7-sulfonic acid. 7 1-amino-8-hydroxynaphthalene-4-sul- OCH; 2-amino-1-hydroxybenzene-4-su1fonic acid- (2-hydroxy)-ethy1am.lde (acid) Z-phenylionic acid. amino-5-hydroxynaphtha1ene-7.4-disu1ionic acid. 8.. 1amino-8-hydroxynaphthalene-3.fi-dl- --OCH;.. 2-amino-1-hydroxybenzene-isnlionic acid-cthylamide- (acid) 2(2-ch1oro)-phenylsulfonic acid. amino-5-hydroxynaphthaIene-7-su1fonic acid. '9 .do -CO0H.. 2-amino-1-hydroxybenzene4-suitonic acid amide-(acid) 2-phenylamino-5-hydroxy,

. naphthalene-7-sulfonic acid. 9. do C,00H.. Zamino-i-hydroxybenzene-4-sulfonic acid methylamide (acid) 2-(4-rnethoxy)- phenylamino-5-hydroxynaphthalenc-7-sulionic acid. -11 dn -.GO0H.. 2-amino-lhydroxy-4nitr0-6-Chl0r0benzene (a0id) 2-(4-ch10ro) phenylamino-5-hydroxynaphthalene-7-sulionic acid. '12 l-amino-8-hydroxynaphthalene-4-sul- 0GH;.. '2-amino-1-hydroxy-4 eh10r0benzene-fi(acid) 2pheny1 1 i l y p t flle etonic acid. 7.4'-disuitonic acid. 13 dn OOH;. 2-arnino-l-hydroxybenzenei-sulfonicacid butylamide-Kadd) 2-phenylamino-5 hydroxynaphthalene-ZW-disulfonic acid. do -0CH 2-amino-l-hydroxybenzene-5-snlfonic acid-Madd .2-(2-methyl) phenylamino-5-hydroxynaohthaleneJ-sulfonic acid. 15 1-arnino-E-hy droxynaphthalene-4.6- COOH.. 2-amino-1-hydroxy-4-ch1orobenzene 5-su1ionicacid- (acid)2-(3-chloro)-pheny1aminodisultonic acid. '5-hydroxynaphthalene-7-sulionic acid. 16., l-arnmo-ifhy Y P OH Z-amino-l-hydroxy-ichloro G-nitrobenzene- (acid)'2-(2-methoxy)-pheny1amin0-5-hydisuliomc acid. droxynaphthalencfl-sulfonic acid. COOH. Z-amino-l-hydroxybenzene-i-sulfomo acid-(2-hydr0xy)propylamidea(acid) 2-,(3-

methyl)-phenylamino 5-hydroxynaphthalene-i -sulfonic acid. 18. OOOH. 2-amino-l-hydroxy-d-nitrobenzenc-dsulionicaeideflacid)2-(4 -Chl010):pheny1amin0 5- hydroxynaphthalene-7-sulionic acid. 11 do -OOOH 2-auripo-1-hydroxybenzene- (acid) z-phenylamino-S hydroXynaphthaiene-7-sulfonic 8.01 2-amino-l-hydroxy-4-nitro-6-carboxybenzene (acid) 2-phenylamino-5hydroxynaphthalene-7-sulfonic acid. 21 fin OOOH 2 amino-1-hydrotry-initrO-B-Garboxybenzene-)(acid)2-(d'rmethyl)-phenylamino-5-hydroxynaphthalene-7-sulfonic acid. 22 do ,OCH 2-amino-l-hydroxybenzeneA-sulfonlc acid-'di-(methyl)-amide- (acid) Z-phenylamino- 5-hydroxynaphthalene'-7.4-disulfonic acid. '23 d0 C0,0H.. 2-amino-l-hydroxybenzene-E-sulionicacid-di-(2'-hydroxyethyl)1 p fi ylamino-5-hydroxynaphthalene-7-sulfonic acid; 1- m{n0-ft-hydr0xynaphtha1cne-4-sul- -O0OH 2-amino-1-hydroxybenzene-4-su1tonic acld-diethy1amlde-. (acid) 2-phenylamlno-5-hyfonlcacli droxynaphthalene-7.3'-disulfonic acid. 25 CO0H.. 2-Tlldiiiod-hylglkoxy-4-mgthylsulfonylbenzene-Kafiid) z-phenylam =fiy y p aene-7-s onic aci 26 .O0OH Z-amino-l-hydroxybenzenei-sulfonic acid amide- (acid) 2-phenylamin0-5-hydr0xynaphthaleneJ-suifonic acid. 27 1-am1no--hydroxynaphthalene-4.6- -COOH.; '2-amino-1-hydroxy-5-nitrobenzene- (acid) Z-phenylamino-5-hydroxynaphthalene-7- disuhomcgacid. sulfonic acid. 38 s--.. 2-arniuo-l-hydroxy-fi-nitrobenzenei-sulfonic acid-*(acid) 2-(4-methyl)-phenylamino- 5-hydroxynaphthalene-7-sulionic acid. --C.0QH.. Z-amino-l-hydroxy-i-chloro-5-nitrobenzene- (acid) 2-phenylamino-5-hydroxyuaphthaiene-7-sulfonlc acid.

5 adding a solution of 2.5 parts of sodiumsulfide'in 12.5 Further polyazo dyestuffs obtainable by the process parts of water at 60. To the solution is then given described in Examples 1 and 2 are tabulated above. 0.7 part of sodium nitrite and it is transferred dropwise The dyestutfs correspond to the general formula: to a mixture of 20 parts of hydrochloric acid and 100 OH NH 7 parts of ice. The mixture containing the resulting di- 5 z (600E azotetrakisazo compound is added to a solution at 10 of 5.2 parts of the monoazo compound obtained by acid RNAGN NmOMN-R coupling of diazotized Z-amino-1-hydroxy-4-methylsulfonylbenzene with 2-phenylamino-5-hydroxynaphthalene yx 7-sulfonic acid, 100 parts of water, 10 parts of 30% 10 sodium hydroxide solution and 25 parts of a. mixture of pyridine bases. After some time the hexakisazo dyeand are characterized by the l-amino-8-hydroxynaphthastuff so formed is completely precipitated from the coulenesulfonic acid used (Column I), the substituent z pling mass by means of common salt, then filtered and (Column II) and the monoazo compound (R-H) from if necessary purified. It is a dark powder which dyes 5 which the radical R is derived (Column III). The cotton and fibers from regenerated cellulose by the aftercoppered dyeings of the new hexakisazo dyestufis are one-bath coppering and twobath aftercoppering processes all gray in shade.

in gray shades of very good fastness to light, washing The following are formulae of representative products and perspiration. of the foregoing examples.

Example 1 OH HO 80 E OCH: HO NH: COOH HOaS- NH SOr-NH:

HOgS- SOaH H!) Example 2 on y HO rho-ms HN- sons 0cm no 11TH: coon HOaS- NH sol-om N=N-N=N N=N-N=N on Hols sons no Example 4 0H i H0 0,1 HN- son: OCH: HO NH, 00011 H0=s- NH No; a N==NON=N N=NON=N- or: EOzS- 80:11 no Example 5 Q 0H t 7 HO 0, COOH H0aS- NE NO:

Example 9 0H t HO HOzS '7 Example 30 parts of pre-wetted cotton are entered into 300 parts of water at 40. The bath is then prepared with a concentrate'd aqueous solution of 0.2 part of the dyestufi obtained according to Example 1 and raised to the boil in 30 minutes. During this time 3 parts of sodium sulfate in the form of a concentrated aqueous solution are added to the dyebath in small portions. The dyebath is maintained at the boil for a further 30 minutes, when 1 partof sodium sulfate is added; it is then cooled slowly to 40. The dyed material is rinsed well and then treated for 30 minutes in a fresh bath at 70 containing 300 parts of water, 0.3 part of acetic acid and 0.2 part of copper sulfate. The dyeing, thus metallized, is finally rinsed and dried.

In place of the 0.2 part of copper sulfate in the aftertreating bath, 0.2 part of a copper complex compound of the condensation product of diethylene triamine and dicyanodiamide can be used.

Having thus disclosed the invention what we claim is:

1. A metallizable hexakisazo dyestuif of the formula OH NH, COOH wherein one x represents hydrogen, the other x being --SO H, y represents a member selected from the group consisting of hydrogen and SO H, z represents a member selected from the group consisting of COOH and OCH and R is the radical of a monoazo compound which corresponds to the formula which couples in the position 6 of the naphthalene nucleus, and wherein v represents a member selected from the group consisting of hydrogen, methyl, methoxy, chlorine and --SO H, w represents a member selected from the group consisting of hydrogen, chlorine, nitro, SO H,

sulfonamido, sulfon(lower alkyl)amido, sulfon(lower hydroxyalkyl)amido, snlfon(di-lower alkyl)amido, sulfon- (di-lower hydroxyalkyl)amido and methylsulfonyl, and t represents a member selected from the group consisting of hydrogen, chlorine, nitro, SO H and COOH when w stands for a member selected from the group consisting of chlorine, nitro and SO H, t and w being difierent from each other except when both stand for hydrogen, and t being hydrogen when w represents a member selected from the group consisting of sulfonamido, sulfon- (lower alkyl)amido, sulfon(lower hydroxyalky1)amido,

sulfon (di-lower alkyl)amido, sulfon(di-lower hydroxyalkyl)amido and methylsulfonyl, the total number of sulfonic acid groups in the hexakisazo dyestufl being at most 6.

on H0 QN=N N=N mN-ogs HN- soua ocHt H0 NH, 0 0 0H Ho1s- NH SDI-NH! N=NC -N=N N=NC -N=N I on H038 som no 3. The metallizable polyazo dyestufi which corresponds to the formula OH HO QN=N N=N nae-ms HN son: 0 OH: HO NH, 00011 nots- NH SOPCHI' N=NN=N- N=NON=N- on 110.8 sou: m

4. The metallizable polyazo dyestufi which corresponds to the formula N=N N=N OgN. HN-- SOzH 0033 H? E Ha COOH H018 NE N0: N=NC -N=N N=N $11 H015 sotn no 9 5. The metallizable polyazo dyestufi which corresponds to the formula o, HN- 50511 C003 no NH,

MOM M on 1:0;5- S0:H

6. The metallizable polyazo dyestufi which corresponds to the formula 0 (g MOM E H0:

C O OH H 0 COOH 110:8-

NH SOr-NH;

7 References Cited in the file of this patent UNITED STATES PATENTS Bossard Bossard et a1 Patent No. 2,958,689

UNITED STATES PATENT OFFICE CERTIFICATION OF CORRECTION November 1, 1960 Hans-Rudolf Bylandamewt al.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 4 lines 15 to 19, the left-hand portion of the formula should appear as shown below instead of as in the patent:

OCH

column 8', lines v5 to 12, the right-hand portion of the formula should appear as vshow-n below instead of as in the patent:

HIIV SO H (SEAL) Attest:

ERNEST W. SWIDER Attesting Officer DAVID L. LADD Commissioner of Patents 

1. A METALLIZABLE HEXAKISAZO DYESTUFF OF THE FORMULA 